posted on 2015-02-19, 00:00authored byKathy
J. Chen, Azzam Charaf-Eddin, Balaji Selvam, Florent Boucher, Adèle D. Laurent, Denis Jacquemin
Because
photochromes act as light-induced molecular switches, there
is considerable interest in exporting their molecular functionality
in the solid state in order to develop photoresponsive materials.
In that context, we have carried out a DFT investigation of a series
of photochromic derivatives of trans/cis-azobenzene and open/closed-diarylethene adsorbed onto rutile (110)
and anatase (101) slabs. By varying the auxochromes and the photochromic
state, we examine the trends in the surface–adsorbate interplay
in terms of the electronic structure, adsorption geometries, and Bader
charge transfer. Using principal components analysis, we demonstrate
how the dipole moment of the isolated photochrome in the direction
of the anchoring group is the most important predictor of the electronic
structure of the adsorbed system. A key point of this paper is to
show how the energy levels of the isolated photochrome and bare slab
change as a result of adsorption and how first-principles modeling
helps to rationalize and predict these trends.